WO2023189866A1

WO2023189866A1 - Laminate

Info

Publication number: WO2023189866A1
Application number: PCT/JP2023/011036
Authority: WO
Inventors: 直樹東
Original assignee: 東洋アルミニウム株式会社
Priority date: 2022-03-30
Filing date: 2023-03-21
Publication date: 2023-10-05

Abstract

[Problem] To provide a laminate that is capable of maintaining good water repellency or oil repellency even after a long period of contact with oil or water. [Solution] A laminate comprising a base material and a functional layer, said laminate being characterized in that (1) the functional layer includes a three-dimensional network structure, and (2) the three-dimensional network structure includes (a) at least one type of functional particles from among (a1) composite particles that have a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles and (a2) hydrophobic particles, and (b) a hydrophobic resin containing fluorine.

Description

laminate

The present invention relates to a novel laminate. More specifically, the present invention relates to a laminate having water repellency and oil repellency.

Water-repellent technology or oil-repellent technology is widely researched for anti-adhesion applications, mold release applications, etc. In particular, for foods, beverages, pharmaceuticals, cosmetics, etc., in order to prevent or suppress the contents from adhering to packaging materials, super water repellent treatment with a contact angle of 150° or more with water or oil Products with super oil-repellent treatment that have a contact angle of 150° or more have also been developed.

For example, a laminate in which a porous functional layer containing a thermoplastic resin and a three-dimensional network structure formed by fine particles having water repellency and/or oil repellency fixed to each other is formed on a base film. , the porous functional layer has a porosity of 1% by volume or more and 50% by volume or less in the region from the bottom of the porous functional layer to 50% thickness in the thickness direction, and A laminate is known that has a porosity of 50% by volume or more and 99% by volume or less in a region between the thickness exceeding 50% and the surface of the porous functional layer (Patent Document 1).

Japanese Patent Application Publication No. 2021-146651

In the conventional technology as described above, since the three-dimensional network structure has a predetermined porosity, fine particles are difficult to fall off, and high water and oil repellency can be exhibited. However, if the three-dimensional network structure is used in contact with oil or moisture for a long period of time, the three-dimensional network structure may be immersed in the oil, resulting in a decrease in water repellency or oil repellency.

Therefore, the main object of the present invention is to provide a laminate that can maintain good water repellency or oil repellency.

As a result of extensive research in view of the problems of the prior art, the present inventor discovered that a laminate having a specific composition and structure can achieve the above object, and has completed the present invention.

That is, the present invention relates to the following laminate.
1. A laminate including a base material and a functional layer,
(1) The functional layer includes a three-dimensional network structure,
(2) The three-dimensional network structure has a function of at least one of (a) (a1) a composite particle having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of an inorganic oxide fine particle, and (a2) a hydrophobic particle. (b) a hydrophobic resin containing fluorine;
A laminate characterized by:
2. 2. The laminate according to item 1, wherein the functional particles are fixed to the three-dimensional network structure by a hydrophobic resin containing fluorine.
3. 2. The laminate according to item 1, wherein the functional layer is supported on the base material by adhering the fluorine-containing hydrophobic resin to the base material and the functional particles.
4. 2. The laminate according to item 1, wherein the functional layer has a specific surface area of 2 to 195 m ² /g.
5. In the functional layer, the porosity in the area from the bottom of the functional layer to 50% thickness is 0 to 45%, and the porosity in the area from the bottom of the functional layer to more than 50% thickness to the surface of the functional layer (the outermost surface) Item 1. The laminate according to Item 1, wherein the amount is 10 to 55%.
6. The ratio of the functional particles to the fluorine-containing hydrophobic resin (excluding the fluorine-containing hydrophobic resin contained in the functional particles) is 1:50 to 20:1 in solid weight ratio. The laminate according to item 1 above.
7. 2. The laminate according to item 1, wherein the fluorine-containing hydrophobic resin is at least one selected from the group consisting of polyfluoroalkyl methacrylate resin, polytetrafluoroethylene, and ethylenetetrafluoroethylene.
8. 2. The laminate according to item 1, wherein the base material is at least one selected from the group consisting of metal foil, metal plate, resin film, resin board, paper, wood board, nonwoven fabric, or a primer coated product thereof.
9. 2. The laminate according to item 1, wherein the inorganic oxide fine particles have an average primary particle diameter of 5 to 50 nm.
10. 2. The laminate according to item 1, wherein the three-dimensional network structure further includes filler particles having an average particle diameter D50 of 5 to 60 μm.
11. A method of manufacturing a laminate including a base material and a functional layer, the method comprising:
(1) forming a fluorine-containing coating film by applying a fluorine-containing coating liquid containing a fluorine-containing hydrophobic resin to a substrate; and (2) forming a fluorine-containing coating film on the fluorine-containing coating film; ) By applying a coating liquid containing at least one functional particle of (a1) composite particles comprising a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles and (a2) hydrophobic particles. A method for producing a laminate, the method comprising the step of forming a coating film containing composite particles.

According to the present invention, it is possible to provide a laminate that can maintain good water repellency and/or oil repellency. That is, it is possible to provide a laminate that is even more excellent in durability of water repellency and/or oil repellency (oil repellency, etc.).

In particular, the laminate of the present invention comprises (a1) composite particles having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles, and (a2) at least one functional particle of hydrophobic particles; (b) Since it contains a three-dimensional network structure containing a hydrophobic resin containing fluorine, it has high water and oil repellency due to the two components of the functional particles and the hydrophobic resin, and the functional particles are three-dimensional. Because it is relatively firmly fixed to the network structure and base material, it is possible to suppress or prevent the functional particles from falling off over time, resulting in high durability in terms of water repellency and/or oil repellency. can do. Therefore, even if it comes into contact with oil or moisture for a long time, it can exhibit high water repellency and/or oil repellency. In particular, even when the functional layer is immersed in oil (for example, oil at a high temperature of 50°C or higher), good water or oil repellency can be obtained, and the effect can be maintained for a relatively long period of time. becomes.

FIG. 1 is a schematic diagram showing an example of the layer structure of the laminate of the present invention. 3 is a cross-sectional image of the laminate of Example 1. 2 is a cross-sectional image of a laminate of Comparative Example 1. It is a binarized image of Example 1. FIG. 4A shows a cross-sectional image of the stack of secondary electron images from an electron microscope, FIG. 4B shows a binarized image of FIG. 4A, and FIG. This is the result of performing a discriminant analysis method after selecting a region.

1. Laminate of the present invention The laminate of the present invention is a laminate including a base material and a functional layer,
(1) The functional layer includes a three-dimensional network structure,
(2) The three-dimensional network structure has a function of at least one of (a) (a1) a composite particle having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of an inorganic oxide fine particle, and (a2) a hydrophobic particle. (b) a hydrophobic resin containing fluorine;
It is characterized by

An example of an embodiment of the laminate of the present invention is shown in FIG. In the laminate 10 of FIG. 1, a functional layer 12 is formed directly on a base material 11. The functional layer 12 includes a three-dimensional network structure 12a, as shown in FIG. Like the functional layer 12 shown in FIG. 1, it may include voids 12b.

The three-dimensional network structure 12a in FIG. 1 includes at least one functional particle of (a1) a composite particle having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of an inorganic oxide fine particle and (a2) a hydrophobic particle. A and a hydrophobic resin containing fluorine (hereinafter abbreviated as "fluorine-containing resin") B. In other words, a three-dimensional network structure is formed by fixing a plurality of functional particles to each other in a manner such that they are bridged by the fluorine-containing resin. In this way, the functional particles are fixed to the three-dimensional network structure by the fluorine-containing resin. Thereby, the functional particles A are fixed to the functional layer 12, and the functional layer 12 is fixed to the base material 11. In other words, the functional layer 12 is supported on the base material by adhering the fluorine-containing resin to the base material 11 and the functional particles A. In this case, even when hydrophobic particles are used as the functional particles, a three-dimensional network structure is formed by similarly fixing a plurality of hydrophobic particles together with the fluorine-containing resin acting as a bridge, resulting in high repellency. Water-based and durable.

As shown in FIG. 1, the plurality of functional particles A (particle group) are configured in a state where they are aggregated with each other mainly through a fluorine-containing resin. In this case, the fluorine-containing resin is interposed between the plurality of functional particles A, but voids 12b may be included between the functional particles within a range that does not impede the effects of the present invention. good. Furthermore, although the functional particles A are usually in indirect contact with each other via the fluorine-containing resin B, the functional particles may be in direct contact with each other as long as the effects of the present invention are not impaired. good.

For example, the structure of Comparative Example 1 is shown in FIG. 3, and a three-dimensional network structure itself made of functional particles is formed. In other words, functional particles (composite particles) stick together mainly due to intermolecular forces to form a three-dimensional network structure (even though the fluororesins on each surface of adjacent functional particles are in contact with each other) They are not bonded (fixed) as if they were bridged.On the other hand, as shown in FIG. ) to form a three-dimensional network structure.In this respect, the three-dimensional network structure according to the present invention is distinguished from a three-dimensional network structure consisting essentially only of functional particles. Hereinafter, each structure of the laminate of the present invention will be explained in detail.

(1) Base material The base material mainly functions as a support layer that supports the functional layer. Therefore, the material is not particularly limited as long as it has such a function, and may include metal foil (e.g. aluminum foil, etc.), metal plate (steel plate, etc.), resin film (e.g. synthetic resin such as polyester, polyethylene, polypropylene, etc.), resin. Examples include boards (for example, synthetic resins such as polyester, polyethylene, and polypropylene), paper, wood boards, nonwoven fabrics, and primer-coated products thereof.

In particular, in the present invention, for example, at least one resin film of polypropylene film, polyethylene film, and polyester film or metal foil (especially aluminum foil) can be suitably used as the base material.

When the base material is a resin film, the resin film may be either a stretched film or an unstretched film. Furthermore, either a uniaxially stretched film or a biaxially stretched film can be used as the stretched film. Further, as the resin film, various types of resin films subjected to surface treatment such as corona treatment can also be used as the base material.

Although the thickness of the base material is not limited, it can be appropriately set depending on, for example, the material of the base material, the use of the laminate of the present invention, etc. When the base material is in the form of a film or the like, the thickness can generally be set appropriately within a range of about 20 to 80 μm, but is not limited thereto.

The surface of the base material (particularly the surface on which the functional layer is laminated) may be subjected to surface treatment. Thereby, the adhesion (adhesiveness) between the base material and the functional layer can be further improved. Examples of the surface treatment include unevenness treatment using an additive (preferably filled particles), unevenness treatment using embossing, and the like. Although the height of the unevenness is not limited, it is particularly preferably about 5 to 60 μm, and more preferably 20 to 50 μm. Here, as the filled particles, filled particles as shown below can also be used.

(2) Functional layer The functional layer is a layer having water repellency and/or oil repellency. A functional layer is formed on at least one surface of the base material.

The functional layer comprises (a) at least one functional particle selected from (a1) a composite particle having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of an inorganic oxide fine particle and (a2) a hydrophobic particle; ) has a three-dimensional network structure containing a hydrophobic resin containing fluorine. By having such a structure, water repellency or oil repellency is exhibited, and adhesion of objects to the functional layer is prevented or suppressed.

The functional layer has a three-dimensional network structure and can take a porous form, so it has a predetermined specific surface area. Although the specific surface area in this case is not limited, it is usually preferable that the specific surface area is about 2 to 195 m ² /g. Therefore, it can be set to about 2 to 55 m ² /g, for example. This can also be an indicator of the degree of bridging between the fluorine-containing resin and the functional particles in the three-dimensional network structure of the functional layer. Note that the specific surface area in the present invention refers to the specific surface area in the BET method (Brunauer-Emmett-Teller method).

The relationship between the structure of the functional layer and the specific surface area will be explained below using specific numerical values as an example for ease of understanding. The specific surface area of the functional layer is maximized when only functional particles are applied to the base material. For example, when the specific surface area is measured by applying only the functional particles to the base material, it is approximately 200 m ² /g. This is because the functional particles form a three-dimensional network structure using only intermolecular forces, and when the porosity is measured using the method described in Test Example 3 below, it is approximately 55%, which is the theoretical state in which the functional layer has the most voids. becomes. Since the functional layer consisting only of functional particles forms a three-dimensional network structure only by intermolecular forces, there is a risk that the functional particles may easily fall off. The critical point is a specific surface area of about 195 m ² /g, and if the specific surface area exceeds this point, about 197 m ² /g, the amount of fluorine-containing resin is insufficient and the possibility that the functional particles will fall off increases.

Further, when the functional layer is composed of only a fluorine-containing resin and no functional particles are present, the surface becomes smooth and has the lowest specific surface area. For example, even if only polyfluoroalkyl methacrylate resin is applied to the base material, the porosity is 0% and the specific surface area is the lowest, about 0.2 m ² /g. In this case, the three-dimensional network structure is almost lost, resulting in a functional layer with a reduced amount of air in the surface layer, and there is a risk that sufficient oil repellency cannot be obtained. Further, the critical point of the specific surface area is about 2 m ² /g, and if it is lower than this, about 1 m ² /g, there will be almost no voids, and there is a risk that the oil repellency or water repellency durability will be poor.

From the above, it can be said that the porosity and specific surface area of the functional layer have a certain correlation. It is said that voids (that is, air spaces) are theoretically the most repellent of substances, and the contact angle with respect to water or oil is thought to be 180°. According to the Cassie-Baxter theory, this mosaic structure of the air layer and solid material is said to depend on the proportion of the air layer and the liquid repellency of the solid material itself.

As mentioned above, even if the porosity is maximized, if the functional particles are formed only by intermolecular forces, the functional particles will easily fall off, so it is necessary to maintain the three-dimensional mesh structure. Matter becomes important. Therefore, in the present invention, a fluorine-containing hydrophobic resin is used to support the functional particles. If a substance other than the above-mentioned fluorine-containing resin is used as the resin that bridges the functional particles, sufficient oil-repellent durability or water-repellent durability cannot be obtained. This is because the surface free energy (surface tension of a solid) of fluorine-containing substances is generally as low as 20 mJ/ ^m2 or less; for example, the surface tension of edible oil used in Test Example 5 described later is 32 mJ/ ^m2 , which is sufficient. This is thought to be because there is a difference in On the other hand, the surface free energy of fluorine-free resins such as olefins and styrene-butadiene rubber is about 30 to 34 mJ/m ² , which is a small difference compared to the surface tension of edible oil, which is 32 mJ/m ² . Therefore, it is thought that it easily gets wet with oil, resulting in poor oil-repellent durability or water-repellent durability. In this respect, the surface free energy of the fluorine-containing resin used in the present invention is generally about 5 to 25 mJ/m ² , and more preferably 5 to 20 mJ/m ² .

Considering oil-repellent durability or water-repellent durability, it is desirable to bridge and reinforce functional particles with a fluorine-containing resin and maintain a predetermined void space. Furthermore, if a hydrophobic resin containing fluorine is not used as such resin, it will be difficult to sufficiently exhibit oil repellency or water repellency. The larger the porosity, the better from the viewpoint of oil repellency or water repellency, but if the porosity is too large, the physical structure tends to become brittle. In this case, the bottom part is filled with a fluorine-containing resin, and even if the porosity is 0%, the oil repellency or water repellency is maintained as long as the porosity of the upper part is 10% or more.

On the other hand, if the porosity at the bottom is 0% and the porosity at the top is 2%, there are too few voids and there is a risk that sufficient oil or water repellency may not be obtained. If the porosity at the bottom is 0% but the porosity at the top is 10%, the desired oil repellency or water repellency can be maintained, although the effect is not high.

Here, the above-mentioned "bottom" refers to a region of the functional layer up to 50% thickness from the bottom surface of the functional layer on the base material side, as shown in FIG. As shown in FIG. 1, the above-mentioned "upper" refers to the area from the bottom of the functional layer to the surface (outermost surface) of the functional layer over 50% of the thickness.

On the other hand, when only functional particles are applied, the porosity becomes maximum at 55% at the bottom and 55% at the top. As mentioned above, since the functional particles are bound together substantially only by intermolecular forces, there is a risk that they will easily fall off. When the porosity is 45% at the bottom and 55% at the top, the oil repellency or water repellency is not sufficient at a critical point, but can be maintained. If the porosity exceeds this, it is presumed that the bridging effect by the fluorine-containing resin is not sufficient, and the porosity is 53% at the bottom and 55% at the top, and there is a possibility that oil repellency or water repellency cannot be maintained. From this point of view, the porosity can be set in the range of about 0 to 45% at the bottom and about 10 to 55% at the top, but it is particularly preferable to set the porosity to 31 to 45% at the bottom and 40 to 55% at the top. More preferably, the ratio is 35 to 41% and the upper part is 44 to 48%. In particular, it is preferable that the functional layer has a gradient structure in which the porosity increases from the bottom to the top. Therefore, it is desirable that the porosity at the top is larger than the porosity at the bottom. For example, the difference between the two [(top porosity) - (bottom porosity)] is usually preferably 3% or more, particularly preferably 4 to 15%.

The ratio of the functional particles and the fluorine-containing resin (excluding the fluorine-containing hydrophobic resin contained in the functional particles) in the three-dimensional network structure is usually 1:50 in solid weight ratio. ~20:1, preferably in the range of 1:30 to 20:1, more preferably in the range of 1:10 to 4:1, and among them 1:3 to 4:1. Most preferably. By setting it within such a range, a three-dimensional network structure in which the functional particles are firmly bridged by the fluorine-containing hydrophobic resin is formed. In this case, as the ratio of fluorine-containing resin increases, and if it exceeds 1:30 and there is too much fluorine-containing resin, the fluorine-containing resin that bridges the functional particles will completely fill the voids between the functional particles. The three-dimensional network structure cannot be maintained. As a result, the physical properties become equal to those obtained when only the fluorine-containing resin is applied to the base material, and sufficient oil repellency or water repellency cannot be obtained. This means that the specific surface area becomes close to the value obtained when a fluorine-containing resin coating is applied to a substrate. On the other hand, if the ratio of functional particles exceeds 20:1 and there are too many functional particles, the coating film approaches only the functional particles, and the fluorine-containing resin cannot bridge the functional particles, making it impossible to obtain sufficient adhesion. First, it is considered that oil repellency or water repellency cannot be exhibited.

(2-1) Hydrophobic Particles As the hydrophobic particles, at least one kind of inorganic oxide particles (powder) such as silicon oxide, titanium oxide, aluminum oxide, zinc oxide, etc. can be used. Among these, silicon oxide particles are more preferred.

In addition, examples of hydrophobic particles include hydrophobic fine particles made by hydrophilic fine particles made hydrophilic by etching, ultraviolet irradiation, blasting, plasma treatment, etc., and made hydrophobic with a silane coupling agent, etc., with hydroxyl groups remaining partially. can also be used. By forming a functional layer with a three-dimensional network structure, these can strongly adhere to the thermosetting resin on the primer layer side and exhibit super water repellency and/or super oil repellency on the other side. can.

The average primary particle diameter of the inorganic oxide particles is preferably 5 to 50 nm, particularly preferably 7 to 30 nm. Note that the primary particle average diameter of the inorganic oxide particles can be measured using a transmission electron microscope or a scanning electron microscope. More specifically, the average primary particle diameter is determined by photographing with a transmission electron microscope or scanning electron microscope, measuring the diameters of 200 or more particles on the photograph, and calculating the arithmetic mean value. be able to.

The nano-level inorganic oxide particles as described above are not limited, and known or commercially available ones can also be used. For example, as for silica, product names "AEROSIL R972", "AEROSIL R972V", "AEROSIL R972CF", "AEROSIL R974", "AEROSIL RX200", "AEROSIL RY200" (manufactured by Nippon Aerosil Co., Ltd.), "AEROSIL L R202 ”, “AEROSIL R805”, “AEROSIL R812”, “AEROSIL R812S” (all manufactured by Evonik Degussa), “Cylohovic 100”, “Cylohovic 200”, “Cylohovic 603” (all manufactured by Fuji Silysia Chemical) Co., Ltd.), etc. Examples of titania include the product name "AEROXIDE TiO ₂ T805" (manufactured by Evonik Degussa). Examples of alumina include fine particles such as product name "AEROXIDE Alu C" (manufactured by Evonik Degussa), which are treated with a silane coupling agent to make the particle surface hydrophobic.

Among these, hydrophobic silica fine particles can be preferably used. In particular, hydrophobic silica fine particles having trimethylsilyl groups on the surface are preferred in that they provide better non-adhesion properties. Commercial products corresponding to this include, for example, the aforementioned "AEROSIL R812" and "AEROSIL R812S" (both manufactured by Evonik Degussa).

The amount of adhering hydrophobic particles (weight after drying) is not limited, but can usually be set within a range of about 0.01 to 100 g/m ² , and particularly preferably 0.01 to 50 g/m ² . It is preferably 0.1 to 50 g/m ² , more preferably 2 to 10 g/m ² .

(2-1) Composite Particles Composite particles are characterized by having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles. That is, they are particles in which a core particle is an inorganic oxide fine particle, and a coating layer containing a polyfluoroalkyl methacrylate resin is formed on the surface of the core particle.

The inorganic oxide fine particles serving as the core particles are not particularly limited, but at least one particle (powder) of silicon oxide, titanium oxide, aluminum oxide, zinc oxide, etc. can be suitably used. Among these, silicon oxide particles are preferred.

Although the size of the inorganic oxide fine particles is not limited, it is usually preferable that the average primary particle size is about 5 to 50 nm, particularly preferably 7 to 30 nm. Note that the above-described average primary particle diameter can be measured using a transmission electron microscope or a scanning electron microscope. More specifically, the average primary particle diameter is determined by photographing with a transmission electron microscope or scanning electron microscope, measuring the diameters of 200 or more particles on the photograph, and calculating the arithmetic mean value. be able to.

As the above-mentioned nano-level inorganic oxide fine particles, known or commercially available ones can be used. Examples of silicon oxide include the product names "AEROSIL 200"("AEROSIL" is a registered trademark. The same applies hereinafter), "AEROSIL 130", "AEROSIL 300", "AEROSIL 50", "AEROSIL 200FAD", "AEROSIL 380" (and above). , manufactured by Nippon Aerosil Co., Ltd.). Examples of titanium oxide include product name "AEROXIDE TiO ₂ T805" (manufactured by Evonik Degussa). Examples of aluminum oxide include the product name "AEROXIDE Alu C 805" (manufactured by Evonik Degussa).

The method for preparing the above-mentioned composite particles is not particularly limited. For example, a polyfluoroalkyl methacrylate resin is used as a coating material for fine particles (powder) of an inorganic oxide, and a coating layer is formed according to a known coating method, granulation method, etc. Just do it. More specifically, composite particles are preferably prepared by a manufacturing method that includes a step of coating inorganic oxide fine particles with a coating liquid in which a liquid polyfluoroalkyl methacrylate resin is dissolved or dispersed in a solvent (coating step). be able to.

As such resin, known or commercially available resins can be used. Commercially available products include, for example, the product name "CHEMINOX FAMAC-6" (manufactured by Unimatec (Japan)), the product name "Zonyl TH Fluoromonomer code 421480" (manufactured by SIGMA-ALDRICH (USA)), and the product name "SCFC-65530". - 66-7'' (manufactured by Maya High Purity Chem (CHINA)), product name ``FC07-04~10'' (Fluory, Inc (USA)), product name ``CBINDEX:58'' (manufactured by Wilshire Chemical Co., Inc. USA ), product name "Asahi Guard AG-E530", "Asahi Guard AG-E060" (both manufactured by Asahi Glass Co., Ltd.), product name "TEMAc-N" (manufactured by Top Fluorochem Co., LTD (CHINA)) ), Product name "ZONYL 7950" (manufactured by SIGMA -RBI (SWITZ)), product name "6100840-6100842" (Weibo Chemcal Co, LTD (CINA)), product name "CB Index: 75" GmbH&CO.KG (GERMANY)), etc.

In the above manufacturing method, a polyfluoroalkyl methacrylate resin that is liquid at room temperature (25° C.) and normal pressure can be suitably used. As such polyfluoroalkyl methacrylate resin, commercially available products such as those mentioned above can also be used. Among these, from the point of view that superior water repellency and oil repellency can be achieved, for example, a) polyfluorooctyl methacrylate, b) 2-N,N-diethylaminoethyl methacrylate, c) 2-hydroxyethyl methacrylate, and d) 2 , 2'-ethylenedioxydiethyl dimethacrylate can be preferably used as the resin. Commercially available products can also be used.

The solvent used in the coating solution is not particularly limited, and in addition to water, organic solvents such as alcohol and toluene can be used; however, in the present invention, it is preferable to use water. That is, it is preferable to use a coating liquid in which a polyfluoroalkyl methacrylate resin is dissolved and/or dispersed in water.

The content of the polyfluoroalkyl methacrylate resin in the above coating liquid is not particularly limited, but it is generally about 10 to 80% by weight, preferably 15 to 70% by weight, and especially 20% by weight. It is more preferable to set it within the range of 60% by weight.

The method of coating the surface of the inorganic oxide fine particles with the coating liquid may be according to a known method, and for example, any of the spray method, dipping method, stirring granulation method, etc. can be applied. In particular, in the present invention, coating by spraying is particularly preferred since it has excellent uniformity.

After coating with the coating liquid, composite particles can be obtained by removing the solvent by heat treatment. The heat treatment temperature is usually about 150 to 250°C, preferably 180 to 200°C. Although the atmosphere for the heat treatment is not limited, an inert gas (non-oxidizing) atmosphere such as nitrogen gas or argon gas is desirable. Further, for example, a series of steps including a coating step and a heat treatment step can be further performed one or more times as necessary. This makes it possible to suitably control the amount of coating.

The surfaces of the composite particles thus obtained have a coating layer containing a polyfluoroalkyl methacrylate resin. By containing such a resin, it is possible to form a strong coating layer with relatively high adhesion on the surface of the particles due to its excellent affinity with the inorganic oxide fine particles, and also to exhibit higher water repellency or oil repellency. be able to.

The amount of composite particles deposited (weight after drying) may be set to an amount sufficient to form a three-dimensional network structure, but it is usually within a range of about 0.01 to 100 g/ ^m2 . In particular, it is preferably about 0.1 to 20 g/m ² , more preferably 0.5 to 10 g/m ² , and most preferably 0.6 to 5 g/m ² .

(2-2) Fluorine-containing resin The fluorine-containing resin forms a three-dimensional network structure together with the functional particles in the functional layer. Since the fluorine-containing resin itself is hydrophobic or oleophobic, it easily repels moisture or materials containing a large amount of moisture. Furthermore, fluorine-containing resins also tend to repel oil or those containing a large amount of oil. Furthermore, in the present invention, the fluorine-containing resin joins the functional particles to each other, so that the fluorine-containing resin and the functional particles form a three-dimensional network structure, and by adopting such a structure, water repellency is achieved. And the oil repellency becomes even higher. Furthermore, it is preferable that the functional particles are supported (fixed) on the base material by the fluorine-containing resin adhering the base material and the functional particles. This allows the functional layer to be more firmly fixed to the base material, resulting in high durability.

The fluorine-containing resin is not limited as long as it contains fluorine and is hydrophobic, and can be appropriately selected from synthetic resins obtained by polymerizing fluorine-containing monomers. These may be homopolymers or copolymers. For example, polyfluoroalkyl methacrylate resin, polytetrafluoroethylene resin (PTFE), ethylenetetrafluoroethylene resin (ETFE), polyvinylidene difluoride resin, ethylene/tetrafluoroethylene copolymer, perfluoroalkoxyalkane resin, tetrafluoroethylene At least one of ethylene/hexafluoropropylene copolymers, tetrafluoroethylene/perfluoroalkyl vinyl ether copolymers, etc. can be mentioned. These properties are not limited, and for example, an aqueous dispersion type can be suitably used.

In particular, the present invention uses polyfluoroalkyl methacrylate resins, polytetrafluoroethylene resins (PTFE), ethylenetetrafluoroethylene resins (ETFE), perfluoroalkoxyalkane resins, and tetrafluoroethylene-hexafluoropropylene copolymers. At least one selected type can be suitably used. Known or commercially available ones can also be used.

Among these, in the present invention, it is preferable to include a polyfluoroalkyl methacrylate resin as the fluorine-containing resin. In particular, when composite particles are used as functional particles, the functional particles and fluorine-containing resin can be combined by containing a fluorine-containing resin in the functional layer that is substantially the same as the coating layer formed on the surface of the inorganic oxide fine particles. It has a higher affinity with the water repellent and oil repellent, and can exhibit higher water repellency and oil repellency. As such resin, the same resins as those mentioned above can be used, and commercially available products can also be used.

The amount of the fluorine-containing resin deposited (weight after drying) may be set to an amount sufficient to form a three-dimensional network structure, but it is usually preferably 0.5 to 30 g/ ^m2 , especially It is more preferably 0.5 to 5 g/m ² , and most preferably 2.5 to 5 g/m ² .

Also, the ratio (weight ratio) of the functional particles (A) and the fluorine-containing resin (excluding the fluorine-containing hydrophobic resin contained in the functional particles) (B) in the three-dimensional network structure. As mentioned above, for example, A:B can be set to about 20:1 to 1:50, and A:B can be set to about 20:1 to 1:30, but is limited to this. Not done. Therefore, for example, the weight ratio of functional particles (A) to fluorine-containing resin (B) can be set to about A:B=1:0.5 to 3.

(2-4) Other components In the present invention, other components may be included in the functional layer (or three-dimensional network structure) within a range that does not impede the effects of the present invention. Examples include additives such as filled particles, colorants, dispersants, antisettling agents, and antifoaming agents. The total content of additives in the functional layer is, for example, about 50% by weight or less, and can be, for example, about 0 to 40% by weight, but is not limited thereto.

In particular, packed particles can be suitably used in the present invention. By including the filler particles, it is possible to form a nano-microstructure with the inorganic oxide fine particles and exhibit higher water repellency or oil repellency. As the filled particles, filled particles having an average particle diameter D50 of 5 to 60 μm (preferably 10 to 30 μm) can be suitably used. The material may be either an inorganic material or an organic material, for example, selected from the group consisting of polymethyl methacrylate (PMMA), styrene, low density polyethylene (LDPE), high density polyethylene (HDPE), acrylic resin, silica, and alumina. At least one type of particles (powder) can be mentioned. When blending filled particles, the content is not limited, but it should be such that the ratio of [fluorine-containing resin/(filled particles + fluorine-containing resin)] is 25 to 75% by weight after drying. Preferably, filled particles are included. If the ratio is less than 25% by weight, the fluorine-containing resin may not be able to sufficiently adhere the filled particles to the base material, and the filled particles may easily fall off. Even when the proportion exceeds 75% by weight, for example 100% by weight of the fluorine-containing resin without filler particles, it is possible to obtain the desired oil-repellent durability or water-repellent durability.

2. Method for manufacturing a laminate The laminate of the present invention can be suitably manufactured, for example, by the first to third methods shown below.

The first method involves applying at least one of (1) a composite particle having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of (a1) an inorganic oxide fine particle to a base material, and (a2) a hydrophobic particle. A step of forming a coating film by applying a coating solution containing one type of functional particles and (b) a fluorine-containing resin (coating film forming step), and optionally (2) heat-treating the coating film. This is a manufacturing method including a step (heat treatment step).

The second method includes (1) forming a fluorine-containing coating film by applying a fluorine-containing coating liquid containing a fluorine-containing resin to a substrate (fluorine-containing coating formation step); For the fluorine-containing coating film, at least one of (a1) composite particles having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of the inorganic oxide fine particles and (a2) hydrophobic particles is added to the surface of the inorganic oxide fine particles. Step of forming a functional particle-containing coating film by applying a coating solution containing functional particles (composite particle-containing coating film formation step) and optionally (3) heat-treating the coating film obtained above. This is a manufacturing method including a step (heat treatment step).

The third method includes applying to a base material at least one of (a1) composite particles having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles and (a2) hydrophobic particles. a step of forming a coating film containing functional particles by applying a coating solution containing functional particles (composite particle-containing coating film formation step); (2) applying a fluorine-containing resin to the coating film containing functional particles; A step of forming a fluorine-containing coating film by applying a fluorine-containing coating solution containing the fluorine-containing coating solution (fluorine-containing coating forming step), and optionally (3) a step of heat-treating the coating film obtained above (heat treatment step). This is a manufacturing method including.

Among these, the second method can be more preferably adopted. Thereby, the three-dimensional network structure can be constructed and reinforced while maintaining the voids more reliably (that is, keeping the oil repellency high). Although the reason for this is not certain, it is presumed that the functional particles placed on the fluorine-containing coating absorb the fluorine-containing resin by capillary action and become in a bridging state. As a result, it is possible to more effectively suppress or prevent the functional particles from falling off, and as a result, excellent water-repellent durability or oil-repellent durability can be obtained.

<About the first method>
Coating film forming process In the coating film forming process, (a) (a1) composite particles having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles and (a2) hydrophobic particles are applied to the base material. A coating film is formed by applying a coating liquid containing at least one kind of functional particles and (b) a fluorine-containing resin.

The coating liquid usually contains functional particles, a fluorine-containing resin, and a solvent. The types of functional particles and fluorine-containing resin, their ratio, etc. may be within the ranges described above.

Furthermore, the solvent is not limited and can be appropriately selected depending on the type of fluorine-containing resin used. For example, alcohol solvents (ethanol, methanol, isopropyl alcohol (IPA), hexyl alcohol, etc.), ketone solvents (acetone, ketone, methyl ethyl ketone (MEK), etc.), hydrocarbon solvents (cyclohexane, n-pentane, n-hexane, methyl cyclohexane, etc.) (MCH), etc.), aromatic solvents (toluene, etc.), and glycol solvents (propylene glycol, hexylene glycol, butyl diglycol, pentamethylene glycol, etc.).

The coating liquid may be a solution in which a fluorine-containing resin or the like is dissolved in a solvent, but it is particularly preferably in the form of a dispersion in which functional particles and fluorine-containing resin particles are dispersed in a solvent. As a result, when the coating liquid is applied to the substrate, the functional particles and fluorine-containing resin particles are uniformly applied, so the properties of the functional particles are maintained, and the adhesion between the functional particles is improved. , it is possible to improve the adhesion between the functional layer and the base material. When such a dispersion is applied to a base material, most of the functional particles and fluorine-containing resin particles move downward (in the direction of gravity), so the porosity decreases in the area of the functional layer close to the base material. The porosity is high in the region on the outermost surface side of the functional layer. In this way, a functional layer having a gradient structure can be effectively formed.

The method of applying the coating liquid is not particularly limited, and known methods such as roll coating, various gravure coatings, bar coater, doctor blade coating, comma coater, spray coating, and brush coating can be appropriately employed.

After coating, a drying step may be performed if necessary. The drying method is not particularly limited, and may be either natural drying or heat drying. When drying by heating, the heating temperature is not limited, but is usually about 80 to 140°C, particularly 100 to 120°C. The heating time may be appropriately set depending on the heating temperature and the like, and is usually about 3 to 60 seconds, but is not limited thereto.

Heat Treatment Step In the present invention, the coating film obtained in the coating film forming step can be heat treated in the heat treatment step, if necessary. By heat treatment, the functional particles and the fluorine-containing resin are bonded more firmly in the functional layer, and the fluorine-containing resin and the base material are bonded, thereby improving the adhesion between the base material and the functional layer. An excellent laminate can be obtained. Furthermore, in the heat treatment process, a part of the functional particles and/or fluorine-containing resin can be embedded in the base material, so higher adhesion can be obtained and the base material and the functional layer can be more effectively integrated. It can have a similar structure.

The heat treatment temperature is preferably lower than the heat-resistant temperature of the base material, and is preferably set in a temperature range from the lowest glass transition temperature to about the melting point of the fluorine-containing resin contained in the functional layer. Therefore, for example, if the base material has a heat-resistant temperature of 660°C and the fluorine-containing resin has a glass transition temperature of 100°C and a melting point of 270°C, the heat treatment temperature should be about 100 to 270°C (or, for example, about 150 to 200°C). can do.

Further, the heat treatment time may be set to a time sufficient to obtain the desired adhesion, and can be set to, for example, about 10 seconds to 60 minutes, but is not limited thereto.

<About the second method>
Fluorine-containing coating film forming step In the fluorine-containing coating film forming step, a fluorine-containing coating film is formed by applying a fluorine-containing coating solution containing a fluorine-containing resin to a substrate.

The coating liquid usually contains a fluorine-containing resin and a solvent. The type of fluorine-containing resin, the ratio of the two, etc. can be set as described above. Moreover, the same solvents as those mentioned in the first method can be used.

The coating liquid may be in the form of a solution in which the fluorine-containing resin is dissolved in a solvent, but it is particularly desirable to be in the form of a dispersion in which fluorine-containing resin particles are dispersed in a solvent. Thereby, when the coating liquid is applied to the base film, the fluorine-containing resin particles are uniformly applied, so that the adhesion between the finally formed functional layer and the base material can be further improved.

The coating method is not particularly limited, and known methods such as roll coating, various gravure coatings, bar coater, doctor blade coating, comma coater, spray coating, and brush coating can be appropriately employed. The coating amount can be set to about 0.1 to 60 g/m ² after drying, and can also be set to 0.2 to 50 g/m ² , but is not limited thereto.

After coating, a drying step may be performed if necessary. The drying method is not particularly limited, and may be either natural drying or heat drying. In the case of heating and drying, the heating temperature is not particularly limited, but is usually about 80 to 140°C, particularly 100 to 120°C. The heating time may be appropriately set depending on the heating temperature and the like, and is usually about 3 to 60 seconds, but is not limited thereto.

Functional particle-containing coating film forming step In the functional particle-containing coating film forming step, a coating layer containing a polyfluoroalkyl methacrylate resin is applied to the surface of (a) (a1) inorganic oxide fine particles to the fluorine-containing coating film. A coating film containing functional particles is formed by applying a coating liquid containing at least one functional particle of the composite particles and (a2) hydrophobic particles.

The coating liquid usually contains functional particles and a solvent. The type of functional particles, manufacturing method, etc. are as explained above. Furthermore, the same solvents as those mentioned in the first method can be used. The solid content concentration of the coating liquid can be, for example, within a range of about 20 to 60% by weight, but is not limited thereto.

The coating liquid is preferably in the form of a dispersion in which functional particles are dispersed in a solvent. Thereby, when the coating liquid is applied to the fluorine-containing coating film, the functional particles are uniformly applied, so that the adhesion between the finally formed functional layer and the base material can be further improved. Therefore, in this respect, when composite particles are used as the functional particles, it is desirable to use a solvent that does not dissolve the coating layer of the composite particles.

The method for applying the coating liquid is not particularly limited, and may be carried out in the same manner as the method for forming a fluorine-containing coating film. For example, known methods such as roll coating, various gravure coatings, bar coater, doctor blade coating, comma coater, spray coating, and brush coating can be appropriately employed.

Heat Treatment Step In the present invention, the coating film obtained in the coating film forming step (i.e., the coating film containing the fluorine-containing resin and functional particles) can be further heat-treated, if necessary. By performing the heat treatment, the functional particles and the fluorine-containing resin are bonded more firmly in the porous functional layer, and the fluorine-containing resin and the base material are bonded, so that the base material and the porous functional layer are bonded together. A laminate with excellent adhesion can be obtained. Furthermore, in the heat treatment process, a part of the functional particles and/or fluorine-containing resin can be embedded in the base material, so higher adhesion can be obtained and the base material and the functional layer can be more effectively integrated. It is also possible to have a similar structure.

The heat treatment temperature is preferably lower than the heat-resistant temperature of the base material, and is preferably set in a temperature range from the lowest glass transition temperature to about the melting point of the fluorine-containing resin contained in the functional layer. Therefore, for example, if the base material has a heat resistance temperature of 660°C, and the fluorine-containing resin has a glass transition temperature of 100°C and a melting point of 270°C, the heat treatment temperature should be set to about 100 to 270°C (particularly about 150 to 220°C). It can be done.

<About the third method>
The third method can be carried out in accordance with the second method, except that the order of the fluorine-containing coating film forming step and the functional particle-containing coating forming step of the second method is changed.

3. Use of Laminate The laminate of the present invention can be used in various applications requiring at least one of adhesion prevention performance, antifouling property, water repellency, oil repellency, and the like.

For example, it can be suitably used as a packaging material or container for packaging or sealing foods, medicines, cosmetics, etc. For example, a packaging bag formed using the laminate of the present invention with the functional layer placed on the inside can be filled with various contents to provide a sealed packaged product.

Examples and comparative examples are shown below to explain the features of the present invention more specifically. However, the scope of the present invention is not limited to the examples.

[Example 1]
(1) Coating of fluorine-containing resin A commercially available aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, soft aluminum foil, thickness 30 μm) was used as the base material. In addition, per 100 parts by weight of polyfluoroalkyl methacrylate resin (PFMA) (“AG-E060” manufactured by AGC, surface free energy 14 mJ/m ² , solid content 20% by mass, aqueous dispersion type), which is a fluorine-containing resin. A coating solution (dispersion) was prepared by adding 100 parts by weight of ethanol and stirring thoroughly.
Using the above coating solution, the surface of the aluminum foil was coated with a bar coater #14 to a weight of 5.0 g/m ² after drying, and then heated in an oven at 120°C for 40 seconds. A fluorine-containing coating was formed by evaporating the solvent.
(2) Formation of functional layer (2-1) Preparation of composite particles 100 g of hydrophilic silica particles (product name "AEROSIL 200", manufactured by Nippon Aerosil Co., Ltd., BET specific surface area 200 m ² /g, average primary particle diameter 12 nm) The product was placed in a reaction tank and sprayed with 500 g of a commercially available surface treatment agent while stirring under a nitrogen gas atmosphere, then stirred at 200° C. for 30 minutes, and then cooled. As a result, a powder consisting of composite particles was obtained. In addition, the above-mentioned surface treatment agent includes polyfluorooctyl methacrylate, 2-N,N-diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, and 2,2'-ethylenedioxydiethyl as polyfluoroalkyl methacrylate resin (PFMA). An aqueous dispersion (solid content concentration: 20% by mass) of a copolymer of dimethacrylate was used.
(2-2) Preparation of dispersion containing composite particles A dispersion containing composite particles was prepared by adding and mixing 50 parts by weight of the obtained composite particles to 50 parts by weight of ethanol.
(2-3) Coating of composite particle-containing dispersion The obtained composite particle-containing dispersion was coated on the fluorine-containing coating using bar coater #8, and then coated at 120°C for 40 seconds. A functional layer was formed by drying. The amount of composite particles to be applied in the functional layer was confirmed in advance so that the weight after drying was 2.0 g/m ² by applying the composite particles to another base material using a bar coater under the same conditions. In this way, a laminate in which a functional layer was formed on the surface of the base material was produced.
Here, the manufacturing conditions etc. in Example 1 are also shown in Table 1. Table 1 also shows the manufacturing conditions of the following examples and comparative examples.

[Example 2]
When forming a fluorine-containing coating film, PTFE was added to 100 parts by weight of polyfluoroalkyl methacrylate resin (AG-E060 manufactured by AGC, aqueous dispersion type with surface free energy 14 mJ/m ² and solid content 20% by mass). Put 20 parts by weight of powder ("TLP10F-1" manufactured by Mitsui Chemours Fluoro Products Co., Ltd.) and 100 parts by weight of ethanol into a mixer ("Awatori Rentaro ARV-310" manufactured by Thinky Corporation) and mix for 1 minute and 30 seconds. A laminate in which a functional layer was formed on the surface of the base material was produced in the same manner as in Example 1, except that a coating solution was prepared by mixing at 2,000 rpm, and coating was performed using a #10 bar coater.

[Example 3]
When forming a fluorine-containing coating film, it is filled into 100 parts by weight of polyfluoroalkyl methacrylate resin ("AGE-060" manufactured by AGC, aqueous dispersion type with surface free energy 14 mJ/m ² and solid content 20% by mass). 20 parts by weight of particles ("Miperon (registered trademark) A functional layer was formed on the surface of the substrate in the same manner as in Example 1, except that the coating liquid was prepared by mixing at 2000 rpm for 1 minute and 30 seconds, and coated with bar coater #10. A laminate in which was formed was produced.

[Example 4]
When forming a fluorine-containing coating film, add 100 parts by weight of ethanol to 100 parts by weight of polytetrafluoroethylene ("TLP10F-1" manufactured by Mitsui Chemours Fluoro Products Co., Ltd., surface free energy 5 mJ/m ² ), and add enough A coating solution was prepared by stirring the mixture. After coating with a bar coater #14 using this coating solution, coating was performed on the substrate surface in the same manner as in Example 1, except that the dispersion containing composite particles was dried at 200°C for 60 minutes. A laminate in which a functional layer was formed was produced.

[Example 5]
When forming a fluorine-containing coating film, ethanol was added to 100 parts by weight of a polyfluoroalkyl methacrylate resin (AG-E060 manufactured by AGC, aqueous dispersion type with a surface free energy of 14 mJ/m ² and a solid content of 20% by mass). 200 parts by weight was added and sufficiently stirred to prepare a coating solution. A functional layer was formed on the surface of the substrate in the same manner as in Example 1, except that this coating solution was coated using bar coater #3 to give a weight of 0.5 g/m ² after drying. A laminate in which was formed was produced.

[Example 6]
When forming a fluorine-containing coating film, polyfluoroalkyl methacrylate resin (AG-E060 manufactured by AGC, aqueous dispersion type with a surface free energy of 14 mJ/m ² and a solid content of 20% by mass) was coated with a bar coater #36. After coating to a weight of 15 g/m ² after drying, heat-dry it in an oven at 120°C for 60 seconds to evaporate the solvent, and repeat this twice to give a total weight of 30 g/m ² after drying. A fluorine-containing coating film was formed in the following manner.
Next, the composite particle-containing dispersion was coated using a bar coater #5 so that the coating amount of composite particles was 1.0 g/m ² , and a functional layer was formed by drying at 120° C. for 40 seconds. A laminate in which a functional layer was formed on the surface of the base material was produced in the same manner as in Example 1 except for the following.

[Example 7]
A substrate was coated in the same manner as in Example 1, except that the composite particle-containing dispersion was coated with a bar coater #3, and the coating amount of composite particles after drying was 0.5 g/m ² by weight after drying. A laminate having a functional layer formed on the surface was produced.

[Example 8]
A substrate was coated in the same manner as in Example 1, except that the composite particle-containing dispersion was applied using a bar coater #14, and the coating amount of the composite particles after drying was 5.0 g/m ² by weight after drying. A laminate having a functional layer formed on the surface was produced.

[Example 9]
When forming a fluorine-containing coating film, polyfluoroalkyl methacrylate resin (AG-E060 manufactured by AGC, aqueous dispersion type with a surface free energy of 14 mJ/m ² and a solid content of 20% by mass) was coated with a bar coater #8. A fluorine-containing coating film was formed by applying the coating to a weight of 2.5 g/m ² after drying and then heating and drying it in an oven at 120° C. for 40 seconds.
Next, the composite particle-containing dispersion was coated on the fluorine-containing coating film using a bar coater #36, dried at 120°C for 60 seconds, and coated again using a bar coater #36 at 120°C. After drying under the conditions of ×60 seconds, coating was further performed using a bar coater #20, and the coating amount of the composite particles after drying at 120°C × 60 seconds was 50 g/m ² by weight after drying. produced a laminate in which a functional layer was formed on the surface of the base material in the same manner as in Example 1.

[Example 10]
When forming a fluorine-containing coating film, it is filled to 100 parts by weight of polyfluoroalkyl methacrylate resin (AG-E060 manufactured by AGC, aqueous dispersion type with surface free energy 14 mJ/m ² and solid content 20% by mass). 180 parts by weight of particles ("Technopolymer SBX-17" manufactured by Sekisui Plastics Co., Ltd., polystyrene beads, average particle diameter 17 μm) and 250 parts by weight of ethanol were mixed in a mixer ("Awatori Rentaro ARV-310" manufactured by Thinky Corporation). ) and mixed at 2000 rpm for 1 minute 30 seconds to prepare a coating solution, and coated with bar coater #3 to give a weight of 2.5 g/m ² after drying. A laminate in which a functional layer was formed on the surface of the base material was prepared in the same manner as in Example 1.

[Example 11]
When forming a fluorine-containing coating film, it is filled to 100 parts by weight of polyfluoroalkyl methacrylate resin (AG-E060 manufactured by AGC, aqueous dispersion type with surface free energy 14 mJ/m ² and solid content 20% by mass). 60 parts by weight of particles ("Technopolymer SBX-17" manufactured by Sekisui Plastics Co., Ltd., polystyrene beads, average particle diameter 17 μm) and 120 parts by weight of ethanol were mixed in a mixer ("Awatori Rentaro ARV-310" manufactured by Thinky Corporation). ) and mixed at 2000 rpm for 1 minute 30 seconds to prepare a coating solution, and a functional layer was formed on the surface of the substrate in the same manner as in Example 1, except that it was coated with bar coater #5. A laminate was produced.

[Example 12]
When forming a fluorine-containing coating film, it is filled to 100 parts by weight of polyfluoroalkyl methacrylate resin (AG-E060 manufactured by AGC, aqueous dispersion type with surface free energy 14 mJ/m ² and solid content 20% by mass). 60 parts by weight of particles ("Technopolymer MBX-20" manufactured by Sekisui Plastics Co., Ltd., polymethyl methacrylate resin (PMMA) beads, average particle size 20 μm) and 120 parts by weight of ethanol were mixed in a mixer ("Foaming" manufactured by Thinky Corporation). A coating liquid was prepared on the substrate surface in the same manner as in Example 1, except that the coating liquid was prepared by mixing at 2000 rpm for 1 minute and 30 seconds, and was coated with bar coater #5. A laminate in which a functional layer was formed was produced.

[Example 13]
When forming a fluorine-containing coating film, it is filled to 100 parts by weight of polyfluoroalkyl methacrylate resin (AG-E060 manufactured by AGC, aqueous dispersion type with surface free energy 14 mJ/m ² and solid content 20% by mass). 60 parts by weight of particles ("HS-103" manufactured by Nippon Steel Chemical & Materials Co., Ltd., silica spherical particles, average particle diameter 28 μm) and 120 parts by weight of ethanol were mixed in a mixer ("Awatori Rentaro ARV-310" manufactured by Thinky Corporation). ) and mixed at 2000 rpm for 1 minute 30 seconds to prepare a coating solution, and a functional layer was formed on the surface of the substrate in the same manner as in Example 1, except that it was coated with bar coater #5. A laminate was produced.

[Example 14]
When forming a fluorine-containing coating film, add 100 parts by weight of ethanol to 100 parts by weight of ethylenetetrafluoroethylene (ETFE) ("Z8820X" manufactured by AGC, powder form), which is a fluorine-containing resin, and stir thoroughly. A coating solution was prepared. After coating with a bar coater #14 using this coating solution, coating was performed on the substrate surface in the same manner as in Example 1, except that the dispersion containing composite particles was dried at 200°C for 60 minutes. A laminate in which a functional layer was formed was produced.

[Example 15]
When forming a fluorine-containing coating film, filler particles ("Technopolymer SBX-17" manufactured by Sekisui Plastics Co., Ltd., polystyrene beads) are added to 100 parts by weight of ethylenetetrafluoroethylene ("Z8820X" manufactured by AGC Co., Ltd. in powder form). , average particle diameter 17 μm) and 120 parts by weight of ethanol were placed in a mixer ("Awatori Rentaro ARV-310" manufactured by Thinky Corporation) and mixed at 2000 rpm for 1 minute and 30 seconds to prepare a coating liquid. A functional layer was formed on the surface of the substrate in the same manner as in Example 1, except that it was coated with bar coater #5 and then dried at 200°C for 60 minutes after coating the composite particle-containing dispersion. A laminate was produced.

[Example 16]
As a base material, a CPP film (TAS-0125, manufactured by Taisei Kako Co., Ltd.) with a thickness of 250 μm was used. In addition, when forming a fluorine-containing coating film, per 100 parts by weight of polyfluoroalkyl methacrylate resin (AG-E060 manufactured by AGC, aqueous dispersion type with surface free energy 14 mJ/m ² and solid content 20% by mass). 20 parts by weight of packed particles ("Miperon (registered trademark) A functional layer was formed on the surface of the substrate in the same manner as in Example 1, except that the coating liquid was prepared by mixing at 2000 rpm for 1 minute and 30 seconds and coated with bar coater #10. A formed laminate was produced.

[Example 17]
As a base material, a 100 μm thick PET film (“Emblet SD” manufactured by Unitika) was used. In addition, when forming a fluorine-containing coating film, per 100 parts by weight of polyfluoroalkyl methacrylate resin (AG-E060 manufactured by AGC, aqueous dispersion type with surface free energy 14 mJ/m ² and solid content 20% by mass). 20 parts by weight of packed particles ("Miperon (registered trademark) A functional layer was formed on the surface of the substrate in the same manner as in Example 1, except that the coating liquid was prepared by mixing at 2000 rpm for 1 minute and 30 seconds and coated with bar coater #10. A formed laminate was produced.

[Example 18]
Using a 20 μm thick soft aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30), apply a dispersed CPP coating agent ("Heat Seal Varnish PPX-16", manufactured by T&K TOKA Co., Ltd., solid content 15% by mass) using a bar coater #14. A primer layer was formed on the soft aluminum foil by coating and drying at 150° C. for 60 seconds to form a primer layer in an amount of 3 g/m ² after drying.
When forming a fluorine-containing coating film, it is filled to 100 parts by weight of polyfluoroalkyl methacrylate resin (AG-E060 manufactured by AGC, aqueous dispersion type with surface free energy 14 mJ/m ² and solid content 20% by mass). 20 parts by weight of particles ("Miperon (registered trademark) ) and mixed at 2000 rpm for 1 minute and 30 seconds to prepare a coating solution, and coated on the substrate surface in the same manner as in Example 1, except that this was coated on the primer layer with bar coater #10. A laminate having a functional layer formed thereon was produced.

[Example 19]
(1) Coating of fluorine-containing resin As a base material, commercially available aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, soft aluminum foil, thickness 20 μm) was used. In addition, 100 parts by weight of polyfluoroalkyl methacrylate resin (AG-E060 manufactured by AGC, surface free energy 14 mJ/m ² , solid content 20% by mass, aqueous dispersion type), which is a fluorine-containing resin, was mixed with 100 parts by weight of ethanol. A coating liquid (dispersion liquid) was prepared by adding parts by weight and stirring thoroughly.
Using the above coating solution, coat the surface of the aluminum foil with a bar coater #5 to a weight of 1.0 g/m ² after drying, and then heat in an oven at 120°C for 40 seconds. A fluorine-containing coating film was formed by evaporating the solvent.
(2) Preparation of dispersion containing hydrophobic particles 5 g of hydrophobic particles (product name "AEROSIL R812S" manufactured by Evonik Degussa, BET specific surface area: 220 m ² /g, average primary particle diameter: 7 nm) were dispersed in 100 mL of ethanol. A dispersion containing hydrophobic particles was prepared.
(3) Coating of hydrophobic particle-containing dispersion The obtained hydrophobic particle-containing dispersion was coated on the fluorine-containing coating using a bar coater #8, and then coated at 120°C for 40 seconds. A functional layer was formed by drying. The coating amount of the hydrophobic particles in the functional layer was confirmed in advance so that the weight after drying would be 2.0 g/m ² by coating on another base material with a bar coater under the same conditions. In this way, a laminate in which a functional layer was formed on the surface of the base material was produced.

[Example 20]
Hydrophobic particles were coated onto the fluorine-containing coating film prepared in the same manner as in Example 19 using bar coater #24 so that the weight after drying was 10.0 g/m ² , and then coated at 120°C for 90 seconds. A functional layer was formed by drying under the following conditions.

[Example 21]
Hydrophobic particles were coated on a fluorine-containing coating film prepared in the same manner as in Example 19 using a #24 bar coater so that the weight after drying was 50.0 g/m ² and conditions were applied at 120°C for 90 seconds. A functional layer was formed by repeating the drying step 5 times.

[Example 22]
As a base material, a commercially available aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, soft aluminum foil, thickness 20 μm) was used. Further, the coating solution prepared in Example 19 was coated on the surface of the aluminum foil using a bar coater #24 so that the weight after drying was 15.0 g/m ² , and then heated at 120°C. The film was heated in an oven for 40 seconds, and the above operation was repeated once again to form a fluorine-containing coating film having a dry weight of 30.0 g/m ² .
Next, using the coating solution of Example 19 (2), the hydrophobic particles were coated onto the fluorine-containing coating film using a bar coater 16 so that the weight after drying was 5.0 g/m ² . A functional layer was formed by drying at 120° C. for 90 seconds.

[Comparative example 1]
A laminate was produced in the same manner as in Example 1, except that only the composite particle-containing dispersion liquid was applied to the base material without applying the fluorine-containing resin coating liquid.

[Comparative example 2]
A laminate was produced in the same manner as in Example 1, except that the fluorine-containing resin coating liquid was applied to the base material, and the composite particle-containing dispersion liquid was not applied to the base material.

[Comparative example 3]
When forming a fluorine-containing coating film, a polyfluoroalkyl methacrylate resin (AG-E060 manufactured by AGC, aqueous dispersion type with a surface free energy of 14 mJ/m ² and a solid content of 20% by mass) was coated with a bar coater #36. After coating to a weight of 15 g/m ² after drying, heat drying in an oven at 120°C for 60 seconds to evaporate the solvent, repeating this twice to give a total weight of 30 g/m ² after drying. I made it so that
Next, the composite particle dispersion was diluted with ethanol, coated with bar coater #3 so that the weight of the composite particles after drying was 0.2 g/m ² , and dried at 120°C for 40 seconds. A laminate was produced in the same manner as in Example 1 except that the layers were formed.

[Comparative example 4]
When forming a fluorine-containing coating film, 100 parts by weight of polyfluoroalkyl methacrylate resin (AG-E060 manufactured by AGC Co., Ltd., a surface free energy of 14 mJ/m ² and 100 parts by weight of an aqueous dispersion type with a solid content of 20% by weight) was used. A coating solution was prepared by mixing parts by weight.Using this coating solution, it was coated with a bar coater #3 to a weight of 0.2 g/ ^m2 after drying, and then coated at 120°C. It was dried by heating in an oven for 40 seconds.
Next, the composite particle dispersion was coated using bar coater #36, dried at 120°C for 60 seconds, coated again using bar coater #36, dried at 120°C for 60 seconds, and further A laminate was produced in the same manner as in Example 1, except that the coating was performed using a bar coater #20 and the coating amount of composite particles was 50 g/m ² after drying at 120° C. for 60 seconds. .

[Comparative example 5]
Example 1 Except that maleic anhydride-modified polyolefin resin (MAPO) (290628-2 manufactured by Tanaka Chemical Co., Ltd., surface energy 30 mJ/m ² , solid content 20% by mass) was used as the coating liquid instead of the fluorine-containing resin. A laminate was produced in the same manner as in Example 1.

[Comparative example 6]
Instead ^of coating with a fluorine-containing resin, filler particles ( Put 20 parts by weight of "Miperon (registered trademark) A laminate was produced in the same manner as in Example 1, except that a coating solution was prepared by mixing at 2000 rpm for 1 minute and 30 seconds, and coating was performed using a bar coater #10.

[Comparative Example 7]
Instead of the fluorine-containing resin, styrene-butadiene rubber resin (SBR) ("DYNARON 1320P" manufactured by JSR Corporation) was dissolved in toluene and used as a coating liquid with a solid content of 10% by mass, and coated with a bar coater #20. A laminate was produced in the same manner as in Example 1 except for this.

[Comparative example 8]
A laminate was produced in the same manner as in Example 1, except that acrylic modified polyolefin resin (APO) (300214-1, manufactured by Tanaka Chemical Co., Ltd., solid content 20% by mass) was used as the coating liquid instead of the fluorine-containing resin. did.

[Comparative Example 9]
A 50 μm thick CPP film (P1011 manufactured by Toyobo Co., Ltd.) was used as the base material, and acrylic modified polyolefin resin (APO) (300214-1 manufactured by Tanaka Chemical Co., Ltd., solid content 20% by mass) was coated instead of the fluorine-containing resin. A laminate was produced in the same manner as in Example 1 except that it was used as a working solution.

[Comparative Example 10]
A laminate was produced in the same manner as in Example 19, except that the fluorine-containing resin coating liquid was not applied to the base material, and only the hydrophobic particle-containing dispersion liquid was applied.

[Comparative Example 11]
The same method as in Example 19 was used, except that acrylic modified polyolefin resin (APO) (300214-1, manufactured by Tanaka Chemical Co., Ltd., solid content 20% by mass) was used as the coating solution instead of the fluorine-containing resin coating solution. A laminate was produced.

[Comparative example 12]
As a base material, a commercially available aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, soft aluminum foil, thickness 20 μm) was used. In addition, using a coating liquid in which acrylic modified polyolefin resin (APO) (300214-1 manufactured by Tanaka Chemical Co., Ltd., solid content 20% by mass) was diluted with IPA to give a solid content of 5% by mass, the aluminum was coated with bar coater #3. It was coated onto the foil so that the weight after drying was 0.1 g/m ² .
Next, using the coating solution of Example 19 (2), the hydrophobic particles were coated on the APO coating film with a bar coater #26 so that the weight after drying was 12.5 g/m ² . By drying at 90 seconds at ℃ and repeating the above process twice, a functional layer was formed such that the weight of the hydrophobic particles was 25.0 g/m ² after drying.

[Test Example 1] (Cross-sectional observation)
The obtained laminate was embedded in epoxy resin and cut into cross-sections, and the cross-section of the cut base material was smoothed by irradiating it with an Ar ion beam using an ion milling device (IB-19520CCP manufactured by JEOL Ltd.). A cross section was created. Next, using a scanning electron microscope (“SU8020” manufactured by Hitachi High-Technologies Corporation), we confirmed the formation of a three-dimensional network structure in which the fluorine-containing resin bridged the composite particles at arbitrary locations in plan view. . As an observation example, a cross-sectional image of the laminate of Example 1 is shown in FIG. 2, and a cross-sectional image of the laminate of Comparative Example 1 is shown in FIG.
As a result of observation, if a three-dimensional network structure in which the fluorine-containing resin bridges the functional particles is formed, it is marked as "○", and if such a three-dimensional network structure is not formed, it is marked as "x". Ta. Therefore, for example, when the fluorine-containing resin does not act as a bridge and a three-dimensional network structure is formed only from functional particles, it is marked as "×".

[Test Example 2] (Measurement of specific surface area)
The specific surface area of each laminate sample was measured in the following manner using a NOVA 1000e specific surface area measuring device manufactured by Quantachrome Instruments Corporation according to the static capacitance method defined in Japanese Industrial Standards JIS Z8830:2013. The results are shown in Table 2.
(1) Method for filling laminate The sampling was carried out by cutting a 100 mm long x 100 mm wide laminate into 10 mm widthwise pieces and filling them into a predetermined glass tube. At this time, the material was cut and filled with great care so that the functional layer did not fall off.
(2) Pretreatment of laminate The sample was pretreated at 100° C. for 1 hour under vacuum using the specific surface area measuring device to previously deaerate gases such as water vapor.
(3) Measurement of specific surface area of laminate An adsorption isotherm of the laminate was created under the following conditions.
・Adsorbed gas: High purity compressed nitrogen gas (manufactured by Air Water Nishinippon Co., Ltd., Amagasaki Factory, purity 99.999% or more)
・Adsorption temperature: 77.35K
・Pressure tolerance: 0.100mmHg/0.100mmHg (adsorption/desorption)
・Equilibrium time: 60 seconds/60 seconds (adsorption/desorption)
・Equilibrium timeout: 240 seconds/240 seconds (adsorption/desorption)
・Measurement range: 0.05<relative pressure P/P0<0.3
・Thermal Delay: 180 seconds ・Evacuation Cross-over Pressure: 20mmHg

The specific surface area of the laminate was calculated from the adsorption isotherm of the laminate obtained using the BET multipoint method. At this time, the Correction Coefficient r, which represents the accuracy of the obtained adsorption isotherm, must be a value of 0.9999 or more and the number of measurement plots is 4 or more, and if r is less than 0.9999 even with 4 measurement plots. The test was repeated by increasing the number of samples one by one until r reached a value of 0.9999 or higher.
(4) Calculation of specific surface area of functional layer From the specific surface area St (m ² /g) of the obtained laminate, the specific surface area S (m ² /g) of the functional layer formed on the surface of the base material is calculated as follows: "S=St /(W1/Wt)".
Here, (W1/Wt) is the weight ratio of the functional layer formed on the surface layer of the laminate, Wt is the weight of the laminate, and W1 is "the weight of the laminate - the weight of the base material". In this way, the specific surface area of the functional layer was calculated. The results are shown in Table 2.

[Test Example 3] (Measurement of porosity)
The base material was embedded in epoxy resin, the base material was cut in cross section, and the cross section of the cut base material was smoothed by Ar ion beam irradiation using an ion milling device ("IB-19520CCP" manufactured by JEOL Ltd.). A cross section was created. Next, using a scanning electron microscope (“SU8020” manufactured by Hitachi High-Technologies Corporation), the cross section of the sample was observed under the conditions of an electron emission current of 4300 nA, a working distance of 3.0 mm, and a magnification of 30,000 times. A secondary electron image of 12 μm ² was obtained.
When taking the secondary electron image, the focus was set to the optimum level to avoid astigmatism as much as possible, and the brightness and contrast were adjusted to the optimum appearance to avoid clipping phenomena such as blown out highlights. In addition, the sample was appropriately vapor-deposited using a vapor deposition apparatus (JFC-1600 manufactured by JEOL Ltd.) to prevent the image from becoming blurred due to charging by an electron beam, and then observed. When taking images, the sample position was adjusted so that the functional layer was visible in the entire visual field, assuming that it would be processed appropriately by image processing software. The area from the bottom of the functional layer to 50% thickness was defined as the "bottom", and the area from the bottom of the functional layer to the surface of the functional layer beyond 50% thickness was defined as the "top".
Next, the obtained secondary electron image was binarized using image processing software "WinROOF2018 ver 4.25", and the total number of pixels in the three-dimensional network structure portion in the secondary electron image was measured. The porosity was calculated as "100% - (binarized ratio (%) of the three-dimensional network structure portion)".
Incidentally, the binarization was performed using the automatic binarization system of the software, and after selecting a bright region as an extraction region, a discriminant analysis method was used. Note that the threshold value was not changed in accordance with the automatic binarization system.
In this way, the porosity was calculated from the ratio of the total number of pixels in the three-dimensional network structure to the total number of pixels per 12 μm ² of visual field. The results are shown in Table 2.
This operation was repeated 20 times for each of the bottom and top portions, and the average value was taken as the porosity. As an example, a binarized image of Example 1 is shown in FIG.

[Test Example 4] (Measurement of surface free energy)
The surface free energy of the fluorine-containing resin was measured using a contact angle meter (“DMo-702” manufactured by Kyowa Interface Science Co., Ltd.). The results are shown in Table 2.
The test samples used were coated samples of fluorine-containing resin before coating with functional particle dispersions and the like in Examples and Comparative Examples. The test sample was placed on the stage of a contact angle meter with the fluorine-containing resin coated side facing upward without wrinkles.
Applying the Owens-Wendt theory, we used pure water and diiodomethane as probe liquids, dropped 1 microliter onto the surface of the fluorine-containing resin, and measured the contact angle after 10 seconds using the KYOWA interFAce Measurement and Analysis System FAMAS software. , calculated automatically. These methods were repeated three times and the average value was taken. The surface free energy of the fluorine-containing resins of each Example and Comparative Example was also measured in the same manner. The results are shown in Table 2.

[Test Example 5] (Oil repellency/water repellency)
(1) Oil repellency durability 80 mL of a commercially available edible oil with a known surface tension (manufactured by Nisshin Oilli Group Co., Ltd., Nissin salad oil cholesterol 0, surface tension 32 mJ/m ² ) was placed in a 100 mL glass bottle. Next, this glass bottle was placed in a hot stirrer, a stirrer was inserted, and the bottle was stirred at a speed of 50 rpm until the temperature stabilized at 90°C. Thereafter, the 20 mm x 20 mm sample was fixed with a clip and then immersed in the above-mentioned 90°C edible oil. At this time, the position of the sample was adjusted so that it did not come into contact with the stirrer. Two hours after immersion, the sample was taken out, and commercially available olive oil with a known surface tension (surface tension: 32 mJ/m ² ) was dropped onto the surface of the functional layer, and the state of the droplets was confirmed.
Specifically, the test surface is tilted at an angle of 20 degrees or 45 degrees, and 1 mL of olive oil is dropped, and if all the dropped olive oil rolls even at a 20 degree tilt, it is marked "◎". It is written as "〇" if all of the olive oil that dripped on a 45-degree slope did not roll on a 20-degree slope, and some of the olive oil that dripped on a 45-degree slope rolled. Those in which the dropped olive oil did not roll at all on an inclination of 45 degrees were evaluated as "x". The results are shown in Table 2.
Separately, the above-mentioned edible oil in the glass bottle was heated to 100° C., and the sample was immersed in this edible oil. One hour after immersion, the sample was taken out, and commercially available olive oil with a known surface tension (surface tension: 32 mJ/m ² ) was again dropped on the surface of the functional layer, and the state of the droplets was confirmed. The evaluation method at this time was the same as the above-mentioned case of 90° C. x 2 hours, and evaluation was performed as "◎", "○", "△", and "x". The results are shown in Table 2.
(2) Water repellency durability 80 mL of distilled water was placed in a 100 mL glass bottle. Next, this glass bottle was placed in a hot stirrer, a stirrer was inserted, and the bottle was stirred at a speed of 50 rpm until the temperature stabilized at 80°C. Thereafter, the 20 mm x 20 mm sample was fixed with a clip and then immersed in the above-mentioned 80° C. hot water. At this time, the position of the sample was adjusted so that it did not come into contact with the stirrer. The sample was taken out 30 minutes after immersion, and ion-exchanged water (surface tension: 72 mJ/m ² ) was dropped onto the surface of the functional layer, and the state of the droplets was confirmed.
Specifically, the test surface is tilted at an angle of 20 degrees or 45 degrees, and 1 mL of water droplets are dropped, and if all the dropped water drops roll even at a 20 degree tilt, it is marked as "◎". However, if all of the water droplets that fell on a 45-degree slope did not roll on a 20-degree slope, it is marked as "〇", and those that fell on a 45-degree slope and some of them rolled are marked as "△". ”, and those in which the dropped water droplets did not roll at all when tilted at 45 degrees were evaluated as “×”. The results are shown in Table 2.

As is clear from the results in Table 2, it can be seen that the laminates of Examples 1 to 18 using composite particles can maintain good oil repellency even when immersed in high-temperature oil. From this, it is expected that oil will adhere to the functional layer due to long-term use of the laminate, and even if the functional layer is immersed in oil, it will be able to exhibit high oil repellency.

In particular, among the examples, among those whose surface free energy of fluorine-containing resin has a large difference compared to 32 mJ/ ^m2 of edible oil, and whose specific surface area is close to the value of only inorganic oxide fine particles, functional particles It can be seen that the effect is particularly remarkable when the weight ratio of the fluorine-containing resin and the fluorine-containing resin is 1:3 to 4:1.

Furthermore, it can be seen that the laminates of Examples 19 to 22 using hydrophobic particles can maintain good water repellency even when immersed in hot water.

Claims

A laminate including a base material and a functional layer,
(1) The functional layer includes a three-dimensional network structure,
(2) The three-dimensional network structure has a function of at least one of (a) (a1) a composite particle having a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of an inorganic oxide fine particle, and (a2) a hydrophobic particle. (b) a hydrophobic resin containing fluorine;
A laminate characterized by:
The laminate according to claim 1, wherein the functional particles are fixed to the three-dimensional network structure by a hydrophobic resin containing fluorine.
The laminate according to claim 1, wherein the functional layer is supported on the base material by adhering the fluorine-containing hydrophobic resin to the base material and the functional particles.
The laminate according to claim 1, wherein the functional layer has a specific surface area of 2 to 195 m 2 /g.
In the functional layer, the porosity in the area from the bottom of the functional layer to 50% thickness is 0 to 45%, and the porosity in the area from the bottom of the functional layer to more than 50% thickness to the surface of the functional layer (the outermost surface) The laminate according to claim 1, wherein the laminate is 10 to 55%.
The ratio of the functional particles to the fluorine-containing hydrophobic resin (excluding the fluorine-containing hydrophobic resin contained in the functional particles) is 1:50 to 20:1 in solid weight ratio. The laminate according to claim 1.
The laminate according to claim 1, wherein the fluorine-containing hydrophobic resin is at least one selected from the group consisting of polyfluoroalkyl methacrylate resin, polytetrafluoroethylene, and ethylenetetrafluoroethylene.
The laminate according to claim 1, wherein the base material is at least one selected from the group consisting of metal foil, metal plate, resin film, resin board, paper, wood board, nonwoven fabric, or a primer coated product thereof.
The laminate according to claim 1, wherein the inorganic oxide fine particles have an average primary particle diameter of 5 to 50 nm.
The laminate according to claim 1, wherein the three-dimensional network structure further includes filler particles having an average particle diameter D50 of 5 to 60 μm.
A method of manufacturing a laminate including a base material and a functional layer, the method comprising:
(1) forming a fluorine-containing coating film by applying a fluorine-containing coating liquid containing a fluorine-containing hydrophobic resin to a substrate; and (2) forming a fluorine-containing coating film on the fluorine-containing coating film; ) By applying a coating liquid containing at least one functional particle of (a1) composite particles comprising a coating layer containing a polyfluoroalkyl methacrylate resin on the surface of inorganic oxide fine particles and (a2) hydrophobic particles. A method for producing a laminate, the method comprising the step of forming a coating film containing composite particles.